Zerovalent iron (Fe0)-based Fenton-like technologyhas great potential for treating recalcitrant organic pollutants (ROPs)in wastewater. However, rapidly and precisely manufacturing Fe0-based materials with the desired geometries is challenging. Herein,novel three-dimensional printed Fe0 (3DP-Fe0) and bimetallic 3DP-Ni/Fe0 were customized by 3D printing for efficient Fenton-likedegradation of florfenicol (FLO), a typical antibiotic in wastewater.3DP-Ni/Fe0 with hydrogen peroxide (H2O2) exhibited superiorreactivity toward FLO than 3DP-Fe0, generating hydroxyl radicals(·OH) and atomic hydrogen to achieve >90% dehalogenation and>70% total organic carbon removal within 10 min. The resultingdegradation intermediates possessed lower antibacterial activity thanFLO and did not cause resistance gene proliferation in activated sludge. The Fenton-like activity of 3DP-Ni/Fe0 was similar acrossdifferent shapes but increased with increasing porosity and size. Compared with powdered Ni/Fe0, 3DP-Ni/Fe0 exhibited fasterelectron transfer during Fe(II)/Fe(III) cycling, which increased the utilization efficiency of dissolved Fe2+ and H2O2 for ·OHproduction. Moreover, 3DP-Ni/Fe0 could be reused >150 times, 5-fold more than powdered Ni/Fe0, owing to its lower metal ionrelease and Fe0 depletion. 3DP-Ni/Fe0 with H2O2 can also efficiently remove chemical oxygen demand from real wastewater andother ROPs (e.g., acetaminophen, carbamazepine, thiamphenicol, and tetrabromobisphenol A).
基于零价铁（Fe0）的类芬顿技术在处理废水中的难降解有机污染物（ROPs）方面具有巨大潜力。然而，快速、精确地制造出具有所需几何形状的 Fe0 基材料是一项挑战。与 3DP-Fe0 相比，3DP-Ni/Fe0 与过氧化氢（H2O2）对氟苯尼考（FLO）表现出更高的活性，能在 10 分钟内产生羟基自由基（-OH）和原子氢，实现大于 90% 的脱卤率和大于 70% 的总有机碳去除率。由此产生的降解中间产物的抗菌活性低于 FLO，并且不会引起活性污泥中抗性基因的增殖。不同形状的 3DP-Ni/Fe0 的芬顿类活性相似，但随着孔隙率和孔径的增加而增加。与粉末状 Ni/Fe0 相比，3DP-Ni/Fe0 在 Fe(II)/Fe(III) 循环过程中表现出快速的电子转移，从而提高了溶解的 Fe2+ 和 H2O2 在产生 -OH 过程中的利用效率。此外，3DP-Ni/Fe0 的金属离子释放量和 Fe0 消耗量较低，因此可重复使用 150 次以上，是粉末状 Ni/Fe0 的 5 倍。含有 H2O2 的 3DP-Ni/Fe0 还能有效去除实际废水中的化学需氧量和其他持久性有机污染物（如对乙酰氨基酚、卡马西平、噻吩酚和四溴双酚 A）。
